Method of reclaiming a well completion brine solutions using an organic chelant

ABSTRACT

A method of reclaiming a well completion brine solution by using an organic chelant that is capable of discriminating between (i) iron and/or non-zinc heavy metals; and (ii) calcium and zinc. The chelant is of the formula: 
                         
and may be either a neutral compound, a corresponding salt, or a corresponding quaternary salt, wherein:
         D is F—A (Y 3 ) u (Y 4 ) v ;   R is independently selected from C p  or C p C(O);   C p  is a C 1 –C 36  hydrocarbyl group, optionally substituted with one or more substituents selected the group consisting of halogen, hydroxyl, sulfate, CH 2 CO 2 Z or —(CH 2 ) n PO(OZ) 2  groups;   each A is independently selected from —N and —P;   Y 1  is independently selected from J, —[(F)—A(J)] w Y 6  and R;   J, R 1 , Y 2 , Y 3 , Y 4 , Y 5  and Y 6  are independently selected from the group consisting of —H, R, —(F) n CO 2 Z and —(CH 2 ) n PO(OZ) 2 ;   each F is independently selected from a C 1 –C 12  hydrocarbyl group, optionally substituted with one or more substituents selected the group consisting of halogen, hydroxyl, sulfate, CH 2 CO 2 Z or —(CH 2 ) n PO(OZ) 2  groups;   Z is —H or a balanced counterion of an alkali or alkaline earth metal or NH 4   + ;   m is 0 to 7;   n is 1 to 7;   r+s+t is 1 or 2;   u+v is 1 or 2; and   w is 0 to 7   provided when m is 0, no more than one of R 1 , Y 1 , Y 2  and Y 5  can be —H.

This application is a continuation-in-part application of U.S. patentapplication Ser. No. 10/623,044, filed on Jul. 18, 2003.

FIELD OF THE INVENTION

The present invention relates to the reclamation of oil field completionfluids using an organic chelating agent.

BACKGROUND OF THE INVENTION

High density brines (completion brines) have been widely used in wellcompletion and workover operations in oilfields in the past severaldecades. The completion brines are salt solutions typically having fluiddensities ranging from about 8.4 ppg (pounds per gallon) to about 20ppg. Depending on the density desired, a completion brine can be a onesalt solution (e.g. NaCl, NaBr, CaCl₂, CaBr₂, ZnBr₂ or formate salt inwater), a two salt solution (e.g. CaCl₂/CaBr₂ or ZnBr₂/CaBr₂), or athree salt solution (e.g. ZnBr₂/CaBr₂/CaCl₂). The composition of thebrines determines the fluid properties such as pH, density, etc.Depending on the economics, a fluid can be used in a well and thenpurchased back to be cleaned and reused later.

At the conclusion of any completion or workover project, a substantialvolume of contaminated or unneeded completion/workover fluid typicallyremains. Such fluids may be contaminated with any or all of thefollowing: water, drilling mud, formation materials, rust, scale, pipedope, and viscosifiers and bridging agents used for fluid-loss-controlpills. Depending on their composition and level of contamination, thesefluids may or may not have further practical or economic value. If it isdeemed that the fluids have future use potential, they may be reclaimed.Conversely, if they are determined to have no further use, they must bedisposed of in an environmentally responsible way.

The benefits derived from the use of solids-free fluids, and especiallyhigh-density brines, for completion and workover operations have beenextensively documented in the literature. Unfortunately, the costsassociated with the initial purchase and subsequent disposal of suchbrines has been a hindrance to their universal acceptance especiallysince the “use once and dispose” means of disposal is neither prudentnor economically sound.

Because of the relatively high cost and limited worldwide naturalmineral resources available for producing medium- and high-densitycompletion/workover fluids, it is essential that their used fluids bereclaimed. The reconditioned fluids must meet the same specifications asthose of “new” or “clean” fluids. With respect to completion/workoverfluids, the term “clean” denotes not only the absence of suspendedsolids but also the absence of undesirable colloidal or soluble specieswhich are capable of undergoing adverse reactions with formation,formation fluids or other completion fluids to produceformation-damaging insoluble substances.

There are many known methods for removing contaminates from a brinesolution. One approach is to remove suspended solids by filtration.Simple filtration processes, wherein the brine is filtered through aplate and frame type filter press with the use of a filter aid such asdiatomaceous earth and then through a 2μ cartridge polishing filter, areeffective to remove solid contamination but they have no effect onremoving other types of contamination such as colloidal or solublespecies. This is the case since colloidally dispersed and solublecontaminants cannot be removed by this filtration without first treatingthe fluid to change the chemical and/or physical properties of thecontaminants. The treatments required to salvage the fluid depend on thenature of the contaminants incorporated and their chemical and physicalproperties.

A common contaminant in completion fluids is created by iron. In mostnon-zinc containing brines, it is relatively easy to treat for ironthough careful attention must be made by the analyst. Zinc containinghigh-density brines have proven to be the most difficult to treat foriron removal. Most of the zinc based brines have relatively low pH whichoften leads to high iron contamination during use as completion and/orworkover fluids. Iron contamination in such fluids can reach severalhundred or even thousand milligrams per liter. Further, iron in zincbrine solutions is more likely to be in a soluble and stable form.Because of the low solubility of oxygen in such solutions, a significantpercentage of the iron contaminants exists as ferrous iron. As a result,precipitation of iron hydroxide with the addition of calcium hydroxide,calcium oxide, or other basic material is difficult to achieve becausethe brine is highly buffered through aqueous zinc hydroxide complexes,which makes it nearly impossible to raise the pH appreciably.Additionally the pH of these zinc-containing fluids cannot be adjustedabove about 6.0. Nonetheless, adding lime or other basic (suspended)material to adjust brine pH can be an important step in the reclamationprocess which often consists of multiple steps, including filtration, pHadjustments, oxidation, etc.

One brine reclamation process of the prior art consists of the oxidationof polymeric species to reduce the viscosity and yield point of thecontaminated brine, oxidation of Fe⁺⁺ to Fe⁺⁺⁺ to facilitate removal ofiron, and the oxidation of organic species which interfere with thereclamation process.

Another brine reclamation process of the prior art consists of theinitial filtration of the brine followed by a reduction in the pH of thebrine fluid. Carbon or bentonite absorbent is then added to the brineand the solution is allowed to stand for about six hours. The resultingsolids are then filtered and the pH of the resulting system is slowlyraised. The fluid is then re-filtered and tested for compatibility.

Yet another multi-step reclamation process is disclosed in U.S. patentPub. No. 2002/0130090. In this process, the spent brine is mixed withacid in order to lower the pH. The fluid is then contacted with ahalogen, such as bromine, to increase the density. A reducing agent,such as anhydrous ammonia, is then added. An alkali is then used toneutralize any excess acid. Finally any suspended solid impurities areremoved.

Such multi-step processes for reclaiming brine solutions are flawed.First, such processes often take very long to complete which, in turn,increases expenses as more man-hours and more hours of equipment usageare required to complete the reclamation. They are also expensivebecause they require the addition of multiple chemical agents. In manycases, pH adjustments lead to a reduction in the brine density and areduction in the resale value of the brine. Further, qualityassurance/quality control (QA/QC) is difficult to control in light ofthe multi-steps involved.

Therefore there exists a need for an improved method of reclaiming spentbrine fluid. There is a need for a process that works independent ofproperty changes to the system, such as pH and temperature. In addition,an improved process is needed which is easier to control in QA/QC.

SUMMARY OF THE INVENTION

The present invention relates to a method of reclaiming a wellcompletion brine solution by use of an organic chelant. The organicchelant is capable of discriminating between (i) iron and/or non-zincheavy metals; and (ii) calcium and zinc. The addition of the chelantcauses formation of complex precipitates of the contaminants, which arethen removed.

The organic chelant is of the formula:

and may be either a neutral compound or a corresponding salt, includinga quaternary salt, wherein:

D is F—A(Y³)_(u)(Y⁴)_(v);

R is independently selected from C_(p) or C_(p)C(O);

C_(p) is a C₁–C₃₆ hydrocarbyl group, optionally substituted with one ormore substituents selected from the group consisting of halogen,hydroxyl, sulfate, CH₂CO₂Z or —(CH₂)_(n)PO(OZ)₂ groups;

each A is independently selected from —N and —P;

Y¹ is independently selected from J, —[(F)—A(J)]_(w)Y⁶ and R;

J, R¹, Y², Y³, Y⁴, Y⁵ and Y₆ are independently selected from the groupconsisting of —H, R, —(F)_(n)CO₂Z and —(CH₂)_(n)PO(OZ)₂;

each F is independently selected from a C₁–C₁₂ hydrocarbyl group,optionally substituted with one or more substituents selected the groupconsisting of halogen, hydroxyl, sulfate, CH₂CO₂Z or —(CH₂)_(n)PO(OZ)₂groups;

Z is —H or a balanced counterion of an alkali or alkaline earth metal orNH₄ ⁺;

m is 0 to 7;

n is 1 to 7;

r+s+t is 1 or 2;

u+v is 1 or2; and

w is 0 to 7.

provided when m is 0, no more than one of R¹, Y¹, Y² and Y⁵ can be —H.Such organic chelants are highly effective in precipitating out unwantedimpurities, especially when it contains one or more —(F)_(n)CO₂Z or—(CH₂)_(n)PO(OZ)₂ groups.

DETAILED DESCRIPTION OF THE INVENTION

The organic chelant for use in the invention is capable ofdiscriminating between (i) iron and/or non-zinc heavy metals; and (ii)calcium and zinc. Such chelating agents are capable of optimizing thecomplexation of the targeted metal which translates to greatereffectiveness in removing the metal from the high density brine. Thechelants may be applied to the brine in liquid or powder form.

The functional groups of the chelating agents may dissociate into one ormore multiple anionic or nonionic functional groups. Such anionic ornonionic functional groups may interact with the higher valence statesassociated with transition metals.

The discrimination occurs in light of the differences in the equilibriumconstant between the chelant and iron and non-zinc heavy metals and theequilibrium constant between the chelant and calcium and zinc. Arepresentation of the reactions is as follows:

Where K_(eq1) is greater than K_(eq2), the reaction proceeds withgreater efficiency, thereby resulting in an increase in the number ofchelant-Fe complexes.

The chelating agent for use in the invention generally contains about 4to about 120 carbon atoms, most preferably from about 10 to about 80carbon atoms, and is preferably of the formula:

wherein:

D is F—A(Y³)_(u)(Y⁴)_(v);

R is independently selected from C_(p) or C_(p)C(O);

C_(p) is a C₁–C₃₆ hydrocarbyl group, optionally substituted with one ormore substituents selected the group consisting of halogen, hydroxyl,sulfate, CH₂CO₂Z or —(CH₂)_(n)PO(OZ)₂ groups;

each A is independently selected from —N and —P;

Y¹ is independently selected from J, —[(F)—A(J)]_(w), Y⁶ and R;

J, R¹, Y², Y³, Y⁴, Y⁵ and Y⁶ are independently selected from the groupconsisting of —H, R, —(F)_(n)CO₂Z and —(CH₂)_(n)PO(OZ)₂;

each F is independently selected from a C₁–C₁₂ hydrocarbyl group,optionally substituted with one or more substituents selected the groupconsisting of halogen, hydroxyl, sulfate, CH₂CO₂Z or —(CH₂)_(n)PO(OZ)₂groups;

Z is —H or a balanced counterion of an alkali or alkaline earth metal orNH₄ ⁺;

an alkali or alkaline earth metal or NH₄ ⁺;

m is 0 to 7;

n is 1 to 7;

r+s+t is 1 or 2;

u+v is 1 or 2; and

w is 0 to 7

provided when m is 0, no more than one of R¹, Y¹, Y² and Y⁵ can be —H.Such chelants, as demonstrated in formula (I) may be a neutral compound,a corresponding salt, or a corresponding quaternary salt, such as saltsof an acid containing a cation such as from Group 1, 2, 3, 4, 5, 6, or7, NH₄ ⁺, or a quaternary ammonium group.

A more preferred type of chelant is that represented by formula (I)wherein the C_(p) group of R is a C₁₂–C₂₂ hydrocarbyl group and theformula contains one or more —(F)_(n)CO₂Z or —(CH₂)_(n)PO(OZ)₂ groups.

One preferred type of chelant is that represented by formula (I) whereins and t are both 0 and m is between from 1 to about 7. Such chelantsinclude those of formula (II):

wherein D may represent random repeating blocks of F—A(Y³)_(u)(Y⁴)_(v).Included with this group of chelants are those of formula (III):

wherein R¹ is —H, —(CH₂)_(n)PO(OZ)₂ or —(F)_(n)CO₂Z; and Y³ and Y⁵ areindependently selected from —(F)_(n)CO₂Z, —(CH₂)_(n)PO(OZ)₂ and —H; andk is from 1 to 6, more preferably k is 3. Specific examples of chelantsof formula (III) include those of the structural formulaeR—NH—(CH₂)_(k)—NH₂;

R—N(CH₂COOZ)—(CH₂)_(k)—NH₂; R—N(CH₂COOZ)—(CH₂)_(k)—NH(CH₂COOZ);R—NH—(CH₂)_(k)—NH(CH₂COOZ); R—N(CH₂COOZ)—(CH₂)_(k)—N(CH₂COOZ)₂;R—NH—(CH₂)_(k)—N(CH₂COOZ)_(2,), especially those wherein R is C_(p) orC_(p)C(O); C_(p) having been defined above. In a more preferredembodiment, k is 3 and C_(p) is 12 to 22.

Further preferred as compounds of formula (II) include compounds forformula (VI):

especially wherein Y³ is —H, C_(p) or C_(p)C(O), or —(F)_(n)CO₂Z or—(CH₂)_(n)PO(OZ)₂; and R¹ and Y⁵ are independently selected from—(F)_(n)CO₂Z, —(CH₂)_(n)PO(OZ)₂ and —H; and k is from 1 to 6, preferablywhen k is 3 and C_(p) is 12 to 22.

Included within compounds of formula (VI) are chelants of the structuralformulae R—N (R¹)—(CH₂)_(k)—NH(CH₂COOZ); R—N(R¹)—(CH₂)_(k)—N(CH₂COOZ)₂;R—NH—(CH₂)_(k)—NY⁵(CH₂COOZ); R—N(CH₂COOZ)-(CH₂)_(k)—NHY⁵; andR—N(CH₂COOZ)—(CH₂)_(k)—NY⁵(CH₂COOZ).

Particularly preferred are those organic chelants of the formulaeR—N(R¹)—(CH₂)_(k)—N(CH₂COOZ)₂ and R—N(CH₂COOZ)—(CH₂)_(k)—NY⁵(CH₂COOZ)and R—N (CH₂COOZ)—(CH₂)_(k)—N(CH₂COOZ)₂.

Also suitable compouns are those of formula (I), wherein s, t and m are0.

Such organic chelants include those compounds of formula (IV):

wherein R¹ is —H or —(F)_(n)CO₂Z; Y⁵ is —(F)_(n)CO₂Z. Especiallysuitable are those organic chelants of formula (IV-A):R—NH(CH₂COOZ) or R—N(CH₂COOZ)₂  (IV-A).

Also preferred as organic chelants are those salts wherein s is 0,including the salts of formula (V):

wherein R¹ is C_(p), —(CH₂)_(n)PO(OZ)₂ or —(CH₂)_(n)CO₂Z; each of Y⁴ andY⁵ are independently selected from —H, —(CH₂)_(n)PO(OZ)₂ or—(CH₂)_(n)CO₂Z; X is an anion; and k and n are independently selectedfrom 1 to 6.

The organic chelants for use in the invention may exist in powder form.The powder may be introduced directly into the system or a slurry can bemade which may then be introduced into the brine. In the field,introducing large amounts of powder, while effective, can create dustingproblems. One alternative solution is to form a slurry containing thechelant. Such slurries should be formed from chemically neutral liquidssuch as water, glycols, and brine, preferably brine. The brine can betaken from the brine that needs to be treated or it can be a cleanbrine, such as calcium bromide brine with a density of 14.2 ppg. Theamount of solvent used should be enough to create a slurry and to reducedusting.

After the chelant is introduced into the spent brine, the treated brineis mixed for a time sufficient for the chelant to complex the metal. Thetime that is necessary depends on the amount and type of impurities inthe brine. It is also dependent on the amount of chelant used. A typicalmixing and resting time is from about 12 hours to about six days. Thecomplexed metal may then be removed using known methods.

The chelant may be added with other treatment agents typically used inthe industry. For example, it may be necessary to add an oxidizer to thesystem in order to oxidize iron and other transition metal impurities,or to destabilize interfering organic materials. Iron impurities oftenare present in the ferrous (Fe⁺⁺) state. This state is much more solublethan the ferric (Fe⁺⁺⁺) state. Therefore, in order to improve theeffectiveness of the organic chelant, it may be necessary to add anoxidizer to ensure that the iron is in the ferric state. The oxidizermay be added to the brine with the chelant or may be added to the brineprior to or after the addition of chelant.

Acceptable oxidizers are preferably slow reacting oxidizers, such ascalcium and magnesium peroxide, calcium hypochlorite, oxygen, and otherslightly soluble oxidizing agents. Although all oxidizers capable ofconverting Fe⁺⁺ to Fe⁺⁺⁺ will work within the system, highly soluble,faster reacting oxidizers, such as hydrogen peroxide and sodiumhypochlorite, have a tendency to react with the halides in the brine,which can release the corresponding halogen, especially bromine. Slowreacting oxidizers reduce the release of such halogens, and the amountof vapors passed into the atmosphere.

Other known processes may be used in conjunction with the complexationprocess discussed herein. For instance, it may be necessary to adjustthe pH of the brine. For fluids containing colloidal iron, it is notuncommon to first lower the pH and then raise the pH. For calcium basedfluids, raising the pH is typically achieved by having an excess ofsodium hydroxide, magnesium hydroxide, magnesium oxide, lime, or quicklime suspended in the fluid. Final adjustment to the pH for thereclaimed brine may further be necessary.

Further, the complexation process of the invention may be used inconjunction with the addition of an absorbing or adsorbing material toaugment the reclamation, such as activated carbon or clay.

Further, the process of the invention may further include a step ofintroducing an absorbing, adsorbing or defoaming material to the brinein order to augment the reclamation. Such absorbents, adsorbents anddefoamers function to reduce the level of foaming generated during thereclamation process. Suitable for use as the absorbent are activatedcarbon, carbon black and clay, while suitable defoamers are theconventional defoaming agents including glycols, alcohols including longchain alcohols, silicones, and phosphates like tributylphosphate. Theamount of absorbent or defoamer material added to the brine issufficient to override the foaming nature of the organic chelant.Certain of the organic chelants of the invention are more likely toheavily foam than others. When needed, the amount of absorbent ordefoamer added to the brine is between from about 1 oz. to about 5 lbs.per barrel of brine and may be added to the brine without removal of thecomplexed organic chelant. Typically, the absorbent or defoamer is addedto the brine prior to filtration of the complexed organic chelant.

Another known addition may be that of reducing agents, such as sulfites,to reduce the oxidation state of iron and other metals to destabilizecolloids. This is especially helpful for troublesome brines or to removecolor due to organic species. For example, zinc has been used to reduceiron to iron metal for removal by filtration, and magnesium has beenused to remove trace zinc and iron from brine.

The organic chelant may further be used in conjunction with ashort-chain water-soluble alcohol or alcohol ether. The addition of thealcohol reduces the interfacial tension between the brine and thechelant and thus improves the dispersability of the chelant. Whenemployed, the alcohol is typically present between from about 5 to about30 weight percent based on the total weight of the chelating product andalcohol. Examples of the alcohol include, but are not limited to,ethylene glycol monobutyl ether, ethanol, isopropyl alcohol or mixturesthereof.

The following examples will illustrate the practice of the presentinvention in its preferred embodiments. Other embodiments within thescope of the claims herein will be apparent to one skilled in the artfrom consideration of the specification and practice of the invention asdisclosed herein. It is intended that the specification, together withthe example, be considered exemplary only, with the scope and spirit ofthe invention being indicated by the claims, which follow.

In Examples 1–10, the following mono-, di- and tri-acetic acidderivatives of tallow diamine were employed as sodium salts wherein thetallow amine is derived from a mixture of C₁₄–C₂₂ beef tallow fats.

EXAMPLE 1

A product was prepared as an aqueous solution containing 27% activematerial consisting of the sodium salts of (VI-A), (VI-B), (VI-C),(VI-D), and (VI-E). 0.0447 grams of this product (0.45 ppb) were addedto 35 ml of stirred 16.8 ppg zinc bromide/calcium bromide/calciumchloride brine. The initial iron content was 100 mg/L (50 ppm). Theproduct formed a gelatinous ball on the brine surface, which waspulverized and dispersed with a spatula into the brine vortex. The brinesolution was stirred for 24 hours, after which a sample was taken,filtered, and the iron content in the filtrate was measured. The ironcontent was subsequently measured to be less than 10 mg/L (less than 5ppm).

EXAMPLE 2

A product was prepared as an aqueous solution consisting of sodium saltsof 1.6 wt. percent of (VI-A) and (VI-B), 12.9 wt. percent of (VI-C) and(VI-D), and 11.8 wt. percent of (VI-E). 0.1252 grams of this product(1.75 ppb) were added to 25 ml of stirred 17.4 ppg zinc bromide/calciumbromide/calcium chloride brine. The initial iron content was 450 mg/L(216 ppm). The product formed a gelatinous ball on the brine surface,which was pulverized and dispersed with a spatula into the brine vortex.The brine solution was stirred for 24 hours, after which a sample wastaken, filtered, and the iron content in the filtrate was measured. Theiron content was subsequently measured less than 2 mg/L (1 ppm).

EXAMPLE 3

The product of Example 2 was again synthesized as a 28% active solution,but in a much larger drum batch size, and subsequently tested incontaminated zinc-based high-density brine. 0.2974 grams of the product(2.08 ppb) were added to 50 ml of stirred 16.8 ppg zinc bromide/calciumbromide/calcium chloride brine. The initial iron content was 600 mg/L(298 ppm). The product was added to the vortex and dispersed with aspatula. The brine solution was stirred for 20 hours, after which a 2 mlsample was taken, filtered, and the iron content in the filtrate wasmeasured. The iron content was subsequently measured at 150 mg/L (75ppm). The bulk brine sample was stirred for another 20 hours, afterwhich a 2 ml sample was taken, filtered, and the iron content in thefiltrate was measured. The iron content was subsequently measured at 20mg/L (10 ppm).

EXAMPLE 4

The product of Example 2 was synthesized as a 28% solution in the drumbatch size, and subsequently tested in contaminated zinc-basedhigh-density brine. 0.3419 grams of the product (2.39 ppb) were added to50 ml of stirred 16.8 ppg zinc bromide/calcium bromide/calcium chloridebrine. The initial iron content was 225 mg/L (112 ppm). The product wasadded to the vortex and dispersed with a spatula into the brine vortex.The brine solution was stirred for 16 hours, after which a 2 ml samplewas taken, filtered, and the iron content in the filtrate was measured.The iron content was subsequently measured at 30 mg/L (15 ppm).

EXAMPLE 5

A product was prepared as a 28% aqueous solution similar to thatdescribed in Example 2. 0.1511 grams of this product (2.12 ppb) wereadded to 25 ml of stirred 17.4 ppg zinc bromide/calcium bromide/calciumchloride brine. The initial iron content was 450 mg/L (216 ppm). Theproduct formed a gelatinous ball on the brine surface, which waspulverized and dispersed with a spatula into the brine vortex. The brinesolution was stirred for 24 hours, after which a sample was taken,filtered, and the iron content in the filtrate was measured. The ironcontent was subsequently measured less than 2 mg/L (1 ppm).

EXAMPLE 6

A product was prepared as an aqueous solution consisting of sodium saltsof 2.2 wt. percent of (VI-A) and (VI-B), 8.9 wt. percent of (VI-C) and(VI-D), and 8.0 wt. percent of (VI-E), and containing 17% ethyleneglycolmonobutyl ether. 0.090 grams of the product (0.63 ppb) were added to 50ml of stirred 16.8 ppg zinc bromide/calcium bromide/calcium chloridebrine. The initial iron content was 125 mg/L (62 ppm). The product wasadded to the vortex and dispersed easily and completely into the brine.The brine solution was stirred for 16 hours, after which a sample wastaken, filtered, and the iron content in the filtrate was measured. Theiron content was subsequently measured at 20 mg/L (10 ppm).

EXAMPLE 7

0.158 grams of the product of Example 6 (1.11 ppb) were added to 50 mlof stirred 16.6 ppg zinc bromide/calcium bromide/calcium chloride brine.The initial iron content was 80 mg/L (40 ppm). The product was added tothe vortex and dispersed easily and completely into the brine. The brinesolution was stirred for 16 hours, after which a sample was taken,filtered, and the iron content in the filtrate was measured. The ironcontent was subsequently measured at 2 mg/L (1 ppm).

EXAMPLE 8

0.150 grams of the product of Example 6 (1.05 ppb) were added to 50 mlof stirred 16.4 ppg zinc bromide/calcium bromide/calcium chloride brine.The initial iron content was 150 mg/L (76 ppm). The product was added tothe vortex and dispersed easily and completely into the brine. The brinesolution was stirred for 16 hours, after which a sample was taken,filtered, and the iron content in the filtrate was measured. The ironcontent was subsequently measured less than 2 mg/L (1 ppm).

EXAMPLE 9

0.147 grams of the product of Example 6 (1.05 ppb) were added to 50 mlof stirred 15.7 ppg zinc bromide/calcium bromide/calcium chloride brine.The initial iron content was 125 mg/L (66 ppm). The product was added tothe vortex and dispersed easily and completely into the brine. The brinesolution was stirred for 16 hours, after which a sample was taken,filtered, and the iron content in the filtrate was measured. The ironcontent was subsequently measured at 25 mg/L (13 ppm).

EXAMPLE 10

0.292 grams of the product of Example 7 (2.04 ppb) were added to 50 mlof stirred 17.8 ppg zinc bromide/calcium bromide/calcium chloride brinethat was obtained from the plant in a sealed glass jar. The initial ironcontent was 650 mg/L (305 ppm), essentially all as iron 2+The productwas added to the vortex and dispersed easily and completely into thebrine, after which the glass sample container was immediately sealed.The brine solution was stirred for 31 hours, and the jar was opened onlylong enough to obtain a sample to filter. The iron content in thefiltrate was subsequently measured at 5 mg/L (2 ppm).

EXAMPLE 11

A product was prepared as an aqueous solution containing 28% activematerial containing sodium salts similar in structure to (VI-A) through(VI-E), except that the —CH₂CO₂H groups attached to nitrogen were—CH₂CH₂CO₂H groups. 0.0252 grams of this aqueous solution (0.25 ppb)were added to 35 ml of stirred 16.8 ppg zinc bromide/calciumbromide/calcium chloride brine. The initial iron content was 100 mg/L(50 ppm). The product formed a gelatinous ball on the brine surface,which was pulverized and dispersed with a spatula into the brine vortex.The brine solution was stirred for 24 hours, after which a sample wastaken, filtered, and the iron content in the filtrate was measured. Theiron content was subsequently measured to be less than 10 mg/L (lessthan 5 ppm).

From the foregoing, it will be observed that numerous variations andmodifications may be effected without departing from the true spirit andscope of the novel concepts of the invention.

1. A method of reclaiming a well completion brine comprising the stepsof: (a.) mixing the brine containing metal impurities with a least oneorganic chelant for a time sufficient for the chelant to complex a metaland form a complexed metal precipitate, the organic chelant being aneutral compound or a corresponding salt of the formula:

wherein: D is F—A(Y³)_(n)(Y⁴)_(v); R is independently selected fromC_(p) or C_(p)C(O); C_(p) is a C₁–C₃₆ hydrocarbyl group, optionallysubstituted with one or more substituents selected the group consistingof halogen, hydroxyl, sulfate, CH₂CO₂Z or —(CH₂)_(n)PO(OZ)₂ groups; eachA is independently selected from —N and —P; Y¹ is independently selectedfrom J, —[(F)—A(J)]_(w)Y⁶ and R; J, R¹, Y², Y³, Y⁴, Y⁵ and Y⁶ areindependently selected from the group consisting of —H, R, —(F)_(n)CO₂Zand —(CH₂)_(n)PO(OZ)₂; each F is independently selected from a C₁–C₁₂hydrocarbyl group, optionally substituted with one or more substituentsselected the group consisting of halogen, hydroxyl, sulfate, CH₂CO₂Z or—(CH₂)_(n)PO(OZ)₂ groups; Z is —H or a balanced counterion of an alkalior alkaline earth metal or NH₄ ⁺; m is 0 to 7; n is 1 to 7; r+s+t is 1or 2; u+v is 1 or 2; and w is 0 to 7 provided when m is 0, no more thanone of R¹, Y¹, Y² and Y⁵ can be —H; and (b.) removing the complexedmetal precipitate from the brine wherein the metal impurities containiron and further wherein the complexed metal precipitate contains iron.2. The method of claim 1, wherein s and t are 0 and m is 1 to
 7. 3. Themethod of claim 2, wherein the at least one organic chelant is acompound or a corresponding salt of the formula:

wherein D represents random repeating blocks of F—A (Y³)_(u)(Y⁴)_(v). 4.The method of claim 3, wherein the at least one organic chelant is acompound of the formula:

wherein R¹ is —H, —(CH₂)_(n)PO(OZ)₂ or —(F)_(n)CO₂Z; and Y³ and Y⁵ areindependently selected from —(F)_(n)CO₂Z, —(CH₂)_(n)PO(OZ)₂ and —H; andk is from 1 to
 6. 5. The method of claim 4, wherein k is
 3. 6. Themethod of claim 5, wherein at least one organic chelant is selected fromthe group consisting of: (a.) R—N(CH₂COOZ)—(CH₂)_(k)—NH(CH₂COOZ); (b.)R—N(CH₂COOZ)—(CH₂)_(k)—N(CH₂COOZ)₂; (c.) R—NH—(CH₂)_(k)—N(CH₂COOZ)₂;wherein R is C_(p) or C_(p)C(O).
 7. The method of claim 6, wherein theC_(p) group is selected from C₈ to C₃₆.
 8. The method of claim 7,wherein the C_(p) group is selected from C₁₂ to C₃₆.
 9. The method ofclaim 8, wherein the C_(p) group is selected from C₁₂ to C₂₂.
 10. Themethod of claim 6, wherein k is 3, Z is —H and R is a C₁₄–C₂₂hydrocarbyl group.
 11. The method of claim 4, wherein the at least oneorganic chelant is selected from the group consisting of: (a.)R—N(CH₂COOZ)—(CH₂)_(k)—NH₂; (b.) R—N(CH₂COOZ)—(CH₂)_(k)—NH(CH₂COOZ) (c.)R—NH—(CH₂)_(k)—NH(CH₂COOZ) (d.) R—N(CH₂COOZ)—(CH₂)_(k)—N(CH₂COOZ)₂; (e.)R—NH—(CH₂)_(k)—N(CH₂COOZ)₂; wherein R is C_(p) or C_(p)C(O).
 12. Themethod of claim 11, wherein k is
 3. 13. The method of claim 11, whereink is 3, R is a C₁₄–C₂₂ hydrocarbyl group and Z is —H.
 14. The method ofclaim 3, wherein at least one R¹, Y³ or Y⁵ is —(F)_(n)CO₂Z or—(CH₂)_(n)PO(OZ)₂.
 15. The method of claim 2, wherein the at least oneorganic chelant is a compound of the formula:

wherein Y³ is —H, C_(p) or C_(p)C(O), —(F)_(n)CO₂Z or —(CH₂)_(n)PO(OZ)₂;and R¹ and Y⁵ are independently selected from —(CH₂)_(n)PO(OZ)₂,—(F)_(n)CO₂Z and —H; and k is from 1 to
 6. 16. The method of claim 15,wherein k is
 3. 17. The method of claim 15, wherein the at least oneorganic chelant is selected from the group consisting of: (a.) R—N(R¹)—(CH₂)_(k)—NH(CH₂COOZ); (b.) R—N (R¹)—(CH₂)_(k)—N(CH₂COOZ)₂; (c.)R—NH—(CH₂)_(k)—NY⁵(CH₂COOZ); (d.) R—N(CH₂COOZ)—(CH₂)_(k)—NHY⁵; (e.)R—N(CH₂COOZ)—(CH₂)_(k)—NY⁵(CH₂COOZ).
 18. The method of claim 17, whereinthe at least one organic chelant is selected from the group consistingof R—NR¹—(CH₂)_(k)—N(CH₂COOZ)₂; R—N(CH₂COOZ)—(CH₂)_(k)—N(CH₂COOZ)₂; andR—N(CH₂COOZ)—(CH₂)_(k)—NY⁵(CH₂COOZ).
 19. The method of claim 17, whereineach Z is —H.
 20. The method of claim 17, wherein R¹ is —(F)_(n)CO₂Z or—H.
 21. The method of claim 2, wherein the at least one organic chelantis a compound of the formula:

wherein Y³ is —H, C_(p) or C_(p)C(O), —(F)_(n)CO₂Z or —(CH₂)_(n)PO(OZ)₂;and R¹ and Y⁵ are independently selected from —(F)_(n)CO₂Z,—(CH₂)_(n)PO(OZ)₂ and —H; k is from 1 to 6; and at least one R¹, Y³ orY⁵ is —(F)_(n)CO₂Z or —(CH₂)_(n)PO(OZ)₂.
 22. The method of claim 1,wherein s, t and m are
 0. 23. The method of claim 22, wherein the atleast one organic chelant is a compound of the formula:

wherein R¹ is —H, —(CH₂)_(n)PO(OZ)₂ or —(F)_(n)CO₂Z; and Y⁵ is—(F)_(n)CO₂Z or —(CH₂)_(n)PO(OZ)₂.
 24. The method of claim 23, whereinthe at least one organic chelant is a compound of the formula:R—NH(CH₂COOZ) or R—N(CH₂COOZ)₂.
 25. The method of claim 1, wherein theat least one organic chelant is a salt and further wherein s is
 0. 26.The method of claim 25, wherein the salt is a compound of the formula:

wherein R¹ is —H, C_(p), —(CH₂)_(n)PO(OZ)₂ or —(CH₂)_(n)CO₂Z; each of Y⁴and Y⁵ are independently selected from —H, —(CH₂)_(n)PO(OZ)₂ or—(CH₂)_(n)CO₂Z; X is an anion; and k and n are independently selectedfrom 1 to
 6. 27. The method of claim 1, further comprising adding to thebrine an absorbent, adsorbent or defoamer in an amount sufficient toreduce foaming.
 28. The method of claim 1 wherein at least one J, R¹,Y², Y³, Y⁴, Y⁵ or Y⁶ is —(F)_(n)CO₂Z or —(CH₂)_(n)PO(OZ)₂.
 29. A methodof reclaiming a well completion brine comprising the steps of: (a.)mixing the brine containing metal impurities with an organic chelant fora time sufficient for the chelant to complex a metal and form acomplexed metal precipitate, wherein the organic chelant is at least onemember selected from the group consisting of R—N(R¹)—(CH₂)_(k)—N(CH₂COOZ)₂; R—N(CH₂COOZ)—(CH₂)_(k)—N(CH₂COOZ)₂; andR—N(CH₂COOZ)—(CH₂)_(k)—NY⁵(CH₂COOZ) wherein R is independently selectedfrom C_(p) or C_(p)C(O); C_(p) is a C₁₂–C₃₆ hydrocarbyl group,optionally substituted with one or more substituents selected from thegroup consisting of halogen, hydroxyl, sulfate, CH₂CO₂Z or—(CH₂)_(n)PO(OZ)₂ groups; R^(1 and Y) ⁵ are independently selected from—H, R, —(F)_(n)CO₂Z or —(CH₂)_(n)PO(OZ)₂; each F is independentlyselected from a C₁–C₁₂ hydrocarbon group, optionally substituted withone or more substituents selected the group consisting of halogen,hydroxyl, sulfate, CH₂CO₂Z or —(CH₂)_(n)PO(OZ)₂ groups; Z is —H or abalanced counterion of an alkali or alkaline earth metal or NH₄ ⁺; n is1 to 7; and k is from 1 to 6; and (b.) removing the complexed metalprecipitate from the brine wherein the metal impurities contain iron andfurther wherein the complexed metal precipitate contains iron.